Compound resinous substance and process of making same



Patented Apr. 10, 1928.

UNITED STATES PATENT OFFICE.

JOHN P. TBICKEY, OF 'EVANSTON, AND CARL S. MINER, OF CHICAGO, ILLINOTC, AS- SIGNOBS TO THE QUAKIEB OATS COMPANY, OF CHICAGO, ILLINOIS, A. CORPORA- TION OF NEW JERSEY.

COMPOUND RESINOUS'SUBSTANCE AND PROCESS OF MAKING SAME.

No Drawing. Application filed August 23, 19%, Serial No. 733,782. Renewed February 27, 1928.

This invention pertains to newly discovered resinous substances and relates more particularly to products that we have obtained from alcoholic furane derivatives and aldehydic furane derivations, and to methads? of making such products.

I Furfuralcohol, furfural and other furane derivatives have heretofore been resinified and the resulting products possess properties which are satisfactory and commercially useful for many purposes. Resinification of these materials may be caused to take place by the useof heat or catalysis or both. Un-

der carefully controlled conditions theformation of certain of these resins may be gradual, the products being first semi-liquid and as the reactions proceed viscous and plastic resinous substances result, the consistency of which depends upon the extent to which the reaction has proceeded. Finally,

if the reactions proceed to a conclusion, substantially iiifusible,insoluble, solid, resinous products are obtainable. We 1 have found that the resinification of furfuralcohol particularly may be readily controlled and that intermediate resinous products of various degrees of consistency may be' produced from this particular furane derivative w thout difliculty by our processes. According- 50 ly, the furfuralcohol resins are especially desirable commercially in that their. several forms in various degrees of consistency are adaptable to many uses and may be readily mixed with other compounds or fillers. The

tacky and plastic properties of the furfuralcohol resins in their intermediate stages also render them commercially desirable.

. In this invention, it is one of our objects,

) therefore, to provide a relatively inexpensive 40 resin having desirable properties similar to those of furfuralcohol-resin. Furthermore,

it is our aim to provide a wider field of use to other resinous products of furane derivatives, particularly the resinous products of furfural, by imparting thereto many of the desirable characteristics of the furfuralcoliol resin. I

The invention embodies the discovery of a new type of compound resinous substances which we have found to possess many of the desirable properties above referred to. The

compound resin embodying our invention is comparatively cheap-to produce and under most conditions in its intermediate resins of various degrees of consistency ranging from semi-liquid, syrupy substances to the thick plastic forms, which are relatively stable.

Furthermore, it is the purpose of this invention to provide rapid, inexpensive and eflicient processesifor making resinous materials having the above described properties in a high degree of purityand with carefully controlled compositions.

We have found that resins having various properties may be obtained by resinifying .a mixture or solution of a plurality of furane derivatives. For example,

furfuralcohol may be dissolved in furfural and thereupon both the alcohol and aldehyde may be resinified by catalysis, or by heating, or both. A comparatively inexpensive and plastic resin may be formed by dissolving a quantity of the furfuralcohol in an equal quantity of furfural, and thereupon a quantity of hydrochloric acid equal to one-tenth of one percent by weight of the solutionmay be added while heating the solution to a temperature approximating 80 C. The acid serves as a catalyst and brings about various reactions resulting in resinification of both the alcohol and furfural. The speed and extent to which the action then proceeds may be largely controlled as desired by properly regulating the temperature. The reaction being somewhat exothermic in character will proceed of itselfafter the mixture is heated to approximately 80 C. In treating large volumes of the mixture,as soon as the reaction starts, we preferably control the temperature by applications of a cooling medium. We have found it desirable to-main tain the temperature at about 110 C. or less.

. gradually, thus permitting the formation of I This may be done by the use of refrigerating coils within or around the container.

Another convenient way of producing this com ound resinous material under easily regu ated conditions of temperature 1s to heat thefurfuralcohol-aldehyde mlxture or solution with a quantity ofwater. For example, 250 grams of furfuralcohol and 250 grams of furfural may be mixed w1th 750 grams of water'contalnin about grams of hydrochloric acid and heated wlth constant agitation. When the temperature of this'mixture rises to 80 C., the compound resin begins to form. When the reaction has proceeded to a point where res1n of the desired consistency is obtained the water may be separated and the catalyst may be washed from the resin, preferably with a very weak alkaline solution. Extremely viscous, tacky but relatively stable reslns ma be obtained by this process.

With certain catal sts the process may be efiiciently and rapidly carried out by heating the reaction mixture under pressure to temperatures above the atmospheric boiling point of the furane deriyatives.

Aside from the control of the reaction regulation of the temperature, we have found that the speed and extent ;of the reaction may be controlled by varying'the percentage of catalyst present. For exam, ple, by adding one percent of theehydrochloric acid the reaction will immediately be manifested by producing a blackening of the mixture. However, the reaction is usually mostreadily controlled with weak acids. The speed of the reaction may be also checked by neutralization, by dilution with an inert liquid, or by removal of the catalyst.

Another satisfactory method of forming compound resins of furane derivatives is tofirst ,forin fulfuralcohol resins by any suitable process. The furfuralcohol resin may be dissolved in a substantially equal quantity' by weight of f-urfural, whereupon the solution may be merely heated to form the compound resin, the alcoholic resin apparently havin a catalytic effect in bringing about resini cation of'the furfural. The vis-- cous, tacky properties of furfuralcohol resin may thus be' effectively imparted to the cheaper furfural resin at small ex use.

The combined furfuralcohol and urfural resins may also be formed bya rocess by which pyromucic acid is also pro uced. By

. such a process approximately 192, parts byweight of furfural may be caused t'oreact -tain 4 poun with 27 arts of sodium hydroxide which is preferab y added in a solution of a strength such that 14. ounds of the solution will cons of sodium hydroxide. This reaction mixture should be kept at a low temperature approximating 15 C. until the reaction is completed. It has been found that under these conditions, furfuralcohol and a sodium salt of yromucic acid are formed as a result of a c emical reaction in-- volving simultaneous oxidation *and reduction. The above quantity of sodium hydroxide is insuflicient to' react with all of the furfural. A portion of the furfural accordingly will remain in the mixture after the sodium hydroxide has entirely reacted.

By means of our process we transform the remaining furfural and the furfuraltities of the salt of the mineral acid will be formed and if the particular chemicals above cited are used, this will be a sodium salt of sulphuric acid, the greater part of which will precipitate at this point. A small quantity of the pyromucic acid which is produced will also precipitate at this point. These precipitatesmay now be separateclfrom" the mixture as by filtering and washing." Up to this time the mixture may beikept at a low temperature.

At this point the resulting mixture contains in the solution considerablequantities of pyromucic acid, furfural and furfuralco 1101, and also contains a small amount of the vmineral acidwhich has been added in quantities slightly in excess of the amount neces-' sary to recover all of the pyronmcic acid from its sodium salt. 7 The exact quantity of furfural contained in the mixture may be fixed by controlling the proportion of sollll) dium hydroxide initially added in order that r acompound resin of the desired composition may be later produced. In orderto resinify the alcohol and furf'ural, the mixture may now be heated to a temperature approximating 80 C. As a result ,of the catallll lytic effect of the mineral acid present .ac-

companied by heating, the furfuralcohol andfurlural undergo reactions which if carried sufliciently far. result in complete resinification. The speed and extent of this resini ficationmay be controlled within wide limits by varying the temperature and the amount of mineral acid present, as in the processes previously described. I

After this resinification process has proceeded to the desired extent or when a resin of the desired consistency has been obtained.

the resin may be separated from the liquid mixture and then purified. It will be noted that by this process very eflicient use is made of all of the materials involved.

With all of the above processes in the initlal stages of the resinification, the mixtures take on a darker or'blackening appearance. As the reactions proceed, substances in the .nature of resins are formed. These subfurane derivatives. It is to be understood,

however, that by" these terms are meant chemical compounds containing no other ring nucleus except the furane ring as distinguished from furane compounds which are chemicalcompounds containing another ring nucleus or other ring nuclei besides the furane ring.

It will be understood that various changes and substitutes of equivalents may be made without departing from the scope and principle of the invention-set forth in the pended claims. I

Having thus described our invention, what we claim asnew and desire to secure by Letters Patent of the United States, is:

1. The compound resin resulting from the resinification of an alcholic furane deriva-' tive with its corresponding aldehyde by the action of catalysis.

2. .A compound resinous reaction product formed from an alcoholic furane derivative and furfural, both being in solution.

3. The compound fusible soluble resin formed from a plurality of furane derivatives that severally and of themselves are capable of producing resinous reaction products one of which has the property of reducing the rubbery characteristic of thereslnous reaction product resulting from another furane derivative.

4. The compound resinous reaction product of a mixture of an alcoholic furane derivative and an aldehydic furane derivative.

5.. The compound resinous reaction product of furfuralcoh'ol andan aldehydic furane derivative.

6. The compound resinous reaction product of furfural and an alcoholic 'furane derivative. y

7. The compound resin resulting from the resinification of furfuralcohol with fun.

fural by the action of catalysis.

8. The compound resinous reaction product of furfuralcohol and furfural.

9. A fusible soluble furfural-furfuralcohol resin that is transformable to a substantially infusible insoluble material.

10. A com ound viscous resin formed from furfura and furfuralcohol and which is soluble in organic solvents but substantially insoluble in water.

11. A compound fusible soluble resin resulting from heating a mixture of furfural apd furfuralcohol in the presence of a cata yst.

12.; The method of overcoming rubbery non-plastic properties of a furfural resin which comprises associating furfuralcoholresin therewith.

13. The process of obtaining a compound resinous material which comprises heating furfuralcohol with furfural in the presence of a catalyst. I

14. The process of obtaining a compound resin which comprises subjecting alcoholic and aldehydic furane derivatives in solution to catalysis.

15. The process of obtaining a compound resinous material which comprises heatingfurfuralcohol with furfural in the presence of a small amount of acid.

16. The process of obtaining a compound.

resinous material which comprises heating I furfuralcohol with furfura'l in the presence of a small amount of mineral acid.

17. The process of obtaining a compound resin which comprises subjecting a solution of a plurality of furane derivatives to eatalysis, said furane derivatives severally and of themselves being capable of producing by themselves dissimilar resmous reaction products. 18. The process of obtaining a compound resin, which comprises mixing furfural with a quantit of-an allrali insulficient to convert all the urfural into furfuralcohol and a salt of pyromucic acid, causing the mixture to react to form a mixture of furfural, furfuralcohol and a salt of pyromucic acid, and then adding a quantity of an acid sufiicient to cause liberation of substantially all .of the pyromudic acid and to cause resinification of the furfural and furfuralcohol.

4 19. The compound resin. formed from a reaction mixture which result from reacting furfural with a quantity of'an alkali insufiicient to convert all of the furfural into furfuralcohol and a salt of pyromucic' acid,

adding a quantity of an acid suflicient to cause liberation of-substantially all of the pyromucic acid and to cause resinification of to form the JOHN P. TRICKEY. GARL S. MINER. 

